Gelling agent for oil

ABSTRACT

A compound represented by the following general formula (I), wherein R 1  and R 2  represent a hydrocarbon group having 1 to 26 carbon atoms, preferably a linear or branched alkyl group, R 3  represents a hydrocarbon group having 7 to 10 carbon atoms, preferably a linear or branched alkyl group, n represents 1 or 2 provided that the acidic amino acid residue in the molecule is L-aspartic acid residue when n is 1 and said acidic amino acid residue is L-glutamic acid residue when n is 2, and a gelling agent for an oil comprising said compound.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a gelling agent for an oil. Morespecifically, the present invention relates to a gelling agent for anoil which contains a particular class of an amino acid derivative. Thegelling agent of the present invention is useful for gelling an oil in astate of a liquid at an ordinary temperature to obtain variety forms ofthe oil.

2. Related Art

As gelling agents for an oil that is insoluble in water, for example,polyamide resins, 12-hydroxystearic acid, condensates of an aromaticaldehyde and a polyhydric alcohol whose typical example includesdibenzylidene-D-sorbitol and the like have been known so far. However,these gelling agents have a problem of low solubility in oils. Forexample, gel compositions prepared by using these gelling agents have aproblem of poor stability in a dissolved state, which results information of heterogeneous gel compositions or so-called “sweatingphenomenon” as exudation of the gelled oils form the surfaces of thegels due to degradation with time.

As another gelling agent for an oil, N-lauroyl-L-glutamic aciddibutylamide disclosed in Japanese Patent Unexamined Publication (Kokai)No. 51-19139/1976 is known, and cosmetics containing said substance as agelling agent have been reported. The aforementioned gelling agent canform gels from variety of types of oils. However, gel compositionsobtained sometimes fail to have sufficient gel strength. As a result,when gel compositions are prepared as cosmetics for dermal application,the compositions may sometimes become tender and have a problem from aviewpoint of strength.

Furthermore, U.S. Pat. No. 5,591,424 and International PatentPublication in Japanese (Kohyo) No. 7-506833 disclose antiperspirant gelsticks containing 12-hydroxystearic acid and N-lauroylglutamic aciddibutylamide. However, the aforementioned gel sticks are alsoinsufficient in strength, and the sticks may sometimes have difficultyin application to the skin. Moreover, appearance of each gel compositionobtained by using the gelling agent and an oil is white and lackstransparency, which is not desired from an esthetic viewpoint.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a gelling agent for anoil. More specifically, the object of the present invention is toprovide a gelling agent that has superior gel forming ability for anoil. Another object of the present invention is to provide a gellingagent that enables production of a gel composition having superior gelstrength and transparency. A still further object of the presentinvention is to provide a gel composition which comprises a gellingagent having the aforementioned characteristics and an oil and hassuperior gel strength and transparency.

The inventors of the present invention conducted various studies toachieve the aforementioned objects. As a result, they found that aparticular class of acidic amino acid derivatives had unexpectedlyexcellent properties as a gelling agent for an oil, and gel compositionsprepared from these acidic amino acid derivatives and an oil hadsuperior gel strength and high transparency. They also found that theresulting gel compositions had satisfactory strength for applications ascosmetics, and that the compositions were easily applicable to the skinwhen they are made into a stick form or the like. The present inventionwas achieved on the basis of the aforementioned findings.

The present invention thus provides a compound represented by thefollowing general formula (I):

wherein R¹ and R² independently represent a hydrocarbon group having 1to 26 carbon atoms; R³ represents a hydrocarbon group having 7 to 10carbon atoms; n represents 1 or 2 provided that the acidic amino acidresidue in the molecule is L-aspartic acid residue when n is 1 and saidamino acid residue is L-glutamic acid residue when n is 2.

According to a preferred embodiment of the present invention, providedis the aforementioned compound wherein R¹ and R² independentlyrepresents a linear or branched alkyl group having 1 to 26 carbon atoms;R³ represents a linear or branched alkyl group having 7 to 10 carbonatoms; and n represents 2. According to a more preferred embodiment ofthe present invention, provided is the aforementioned compound whereinR¹ and R² independently represents a linear or branched alkyl grouphaving 3 to 5 carbon atoms, R³ represents a linear or branched alkylgroup having 7 to 9 carbon atoms, and n represents 2. As a particularlypreferred embodiment of the present invention, provided areN-2-ethylhexanoy-L-glutamic acid dibutylamide, N-octanoyl-L-glutamicacid dibutylamide, and N-decanoyl-L-glutamic acid dibutylamide which arecompounds falling within the scope of the aforementioned general formula(I).

From further aspects of the present invention, provided are a gellingagent for an oil which comprises at least one kind of a compoundrepresented by the aforementioned general formula (I); and a gellingagent for an oil which comprises at least one kind of a compoundrepresented by the aforementioned general formula (I) together withN-lauroyl-L-glutamic acid dibutylamide. As preferred examples of thelatter invention, provided is the aforementioned gelling agent wherein aratio of total weight of the compound represented by the aforementionedgeneral formula (I) and weight of N-lauroyl-L-glutamic acid dibutylamideis 35:5 to 5:35.

From still further aspect of the present invention, provided is a gelcomposition which comprises (a) the aforementioned gelling agent, and(b) at least one oil. According to preferred embodiments of theaforementioned gel composition, provided are the gel composition as atranslucent composition, and the gel composition which further comprises(c) at least one active ingredient as an antiperspirant Further, thepresent invention also provides a cosmetic comprising the aforementionedgel composition. Preferably, the cosmetic may be cast in a form of astick.

The present invention further provides a method for gel formation froman oil, which comprises the step of mixing at least one compoundrepresented by the aforementioned general formula (I) with an oiloptionally together with N-lauroyl-L-glutamic acid dibutylamide; amethod for preparing a gel composition comprising an oil which comprisethe step of mixing at least one compound represented by theaforementioned general formula (I) with an oil optionally together withN-lauroyl-L-glutamic acid dibutylamide; and use of the compoundrepresented by the aforementioned general formula (I) for preparation ofa gel composition comprising an oil.

By using the gelling agent of the present invention for an oil, a gelcomposition having high gel strength and superior transparency can beproduced.

PREFERRED EMBODIMENTS OF THE INVENTION

In the general formula (I), R¹ and R² independently represent ahydrocarbon group having 1 to 26 carbon atoms. The hydrocarbon grouprepresented by R¹ or R² may be linear, branched, cyclic, or acombination thereof. As the hydrocarbon group, a hydrocarbon groupcontaining an unsaturated bond may be used; however, an alkyl group maypreferably be used as the hydrocarbon group. A linear or branched alkylgroup having preferably 1 to 10 carbon atoms, more preferably 2 to 6carbon atoms, may be used, and a linear or branched alkyl group having 3to 5 carbon atoms is more preferred. n-Butyl group may most preferablybe used.

R³ represents a hydrocarbon group having 7 to 10 carbon atoms. Thehydrocarbon group represented by R³ may be linear, branched, cyclic, ora combination thereof. As the hydrocarbon group, a hydrocarbon groupcontaining an unsaturated bond may be used; however, an alkyl group maypreferably be used as the hydrocarbon group. As the alkyl group, alinear or branched alkyl group is preferred. More preferably, R³represents a linear or branched alkyl group having 7 to 9 carbon atoms.Examples of the group represented by R³—CO— include, for example,n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoylgroup, 2-ethylhexanoyl group and the like. Among them, octanoyl group,decanoyl group, and 2-ethylhexanoyl group are preferred, and2-ethylhexanoyl group is more preferred from a viewpoint of high gelforming ability for variety of oils. When the group represented byR³—CO— is 2-ethylhexanoyl group, 2-(R,S)-ethylhexanoyl group ispreferably used from a viewpoint of availability of 2-ethylhexanoylchloride as a starting material. In the general formula (I), n ispreferably 2.

In the compound represented by the general formula (I), the acidic aminoacid residue in the molecule is L-aspartic acid residue when n is 1, oracidic amino acid residue is L-glutamic acid residue when n is 2. Thecompound represented by the general formula (I) may have one or moreasymmetric carbons depending on types of R¹, R² and/or R³. Any ofstereoisomers such as optical isomers and diastereomers based on suchasymmetric carbons, any mixtures of the stereoisomers, and racematesfall within the scope of the present invention. Further, when R¹, R²and/or R³ have an olefinic double bond, its configuration may be ineither Z- or E-configuration, and geometrical isomers and any mixturesof the geometrical isomers also fall within the scope of the presentinvention. In addition, any hydrates and any forms of crystals of thecompound represented by the aforementioned general formula (I) also fallwithin the scope of the present invention. As the gelling agent of thepresent invention, any substance such as the aforementioned isomers,mixtures thereof, hydrates thereof and the like can be used.

The compound represented by the general formula (I) can be produced by,for example, reacting a long chain fatty acid halide with L-glutamicacid or L-aspartic acid in the presence of a basic catalyst according tothe Schotten Baumann's reaction to prepare an N-acylated glutamic acidor N-acylated aspartic acid, and then reacting the resulting productwith an amine derivative such as alkylamines in the presence of an acidcatalyst or in the absence of a catalyst with heating. Alternatively,the target compound can be produced by reacting glutamic acid or anaspartic acid with an amine derivative such as alkylamines in thepresence of an acid catalyst or in the absence of a catalyst, and thensubjecting the resulting glutamic acid amide or aspartic acid amide toN-acylation by using an acylating agent such as aliphatic acid halides.

Preparations of the compounds represented by the general formula (I) areexplained specifically and in detail in the examples of thespecification. Therefore, those skilled in the art can produce any ofthe compounds represented by the general formula (I) by referring to thepreparation examples and appropriately choosing starting materials,regents, reaction conditions and the like, and applying appropriatemodifications and alterations to the methods, as required.

As the gelling agent of the present invention, one kind of a compoundselected from the compounds represented by the general formula (I) maybe used. Two or more kinds of compounds selected from the compoundsrepresented by the general formula (I) may also be used in combination.An amount of the gelling agent of the present invention is notparticularly limited so long as the amount is sufficient for gelformation of an oil. Generally, the amount is about 0.1 to 15 parts byweight, preferably 1 to 10 parts by weight based on 100 parts by weightof an oil to be gelled. Where the amount is less than 0.1 part byweight, satisfactory gel strength may sometimes not be obtained. Wherethe amount is more than 15 parts by weight, the agent may not bedissolved in an oil, and appearance of a resulting gelled oil maysometimes be degraded.

The gelling agent of the present invention may containN-lauroyl-L-glutamic acid dibutylamide in addition to one or morecompounds selected from the compounds represented by the general formula(I). Where the aforementioned gelling agent is used, a gel compositionhaving high gel strength and relatively high transparency (translucent)can be obtained. In the aforementioned embodiment, a mixing ratio of thetotal weight of the compound represented by the general formula (I) (asto the term “total weight” used in the specification, when one singlecompound is used, the term means the weight of the compound, or when twoor more compounds are used, the term means the total sum of the weightsof the compounds) and N-lauroyl-L-glutamic acid dibutylamide can besuitably selected depending on desired performances. Generally, theratio may preferably be 35:5 to 5:35. An amount of the gelling agentcontaining N-lauroyl-L-glutamic acid dibutylamide is similar to that ofthe aforementioned gelling agent, and the amount may be 0.1 to 15 partsby weight, preferably 1 to 10 parts by weight based on 100 parts byweight of an oil to be gelled. N-Lauroyl-L-glutamic acid dibutylamideused for the present invention can be produced by the same method as thecompounds represented by the aforementioned general formula (I), or saidcompound can also be obtained as a commercial product from AjinomotoCo., Ltd (trade name: GP-1).

The oil used for the gel composition of the present invention is notparticularly limited so long as the oil sufficiently dissolves theaforementioned gelling agent by heating and forms a gel when cooled toroom temperature. Specific examples thereof include silicone oils;higher alcohols such as cetyl alcohol, isostearyl alcohol, laurylalcohol, hexadecyl alcohol and octyldodecanol; aliphatic acids such asisostearic acid, undecylenic acid and oleic acid; polyhydric alcoholssuch as glycerol, sorbitol, ethylene glycol, propylene glycol andpolyethylene glycol; esters such as myristyl myristate, hexyl laurate,decyl oleate, isopropyl myristate, hexyldecyl dimethyloctanoate,glyceryl monostearate, diethyl phthalate, ethylene glycol monostearateand octyl oxystearate; hydrocarbons such as liquid paraffin, vaselineand squalane; waxes such as lanolin, reduced lanolin and carnauba wax;fats and oils such as mink oil, cacao oil, coconut oil, palm seed oil,camellia oil, sesame oil, castor oil and olive oil; ethylene/a-olefinco-oligomers and the like.

Examples of the silicone oils include silicone oils selected from thegroup consisting of methylpolysiloxane, highly polymerizedmethylpolysiloxane, ether-modified silicones such aspolyoxyethylene/methylpolysiloxane copolymer,polyoxypropylene/methylpolysiloxane copolymer and poly(oxyethylene oroxypropylene)/methylpolysiloxane copolymer, stearoxymethylpolysiloxane,stearoxytrimethylsilane, methyl hydrogen polysiloxane,octamethylpolysiloxane, decamethylpolysiloxane, cyclic silicones such asdecamethylcyclopentasiloxane, octamethylcyclotetrasiloxane,tetrahydrotetramethylcyclotetrasiloxane, methylcyclopolysiloxane,cyclopentasiloxane and dodecamethylcyclohexasiloxane;methylphenylpolysiloxane, trimethylsiloxy silicate, amino-modifiedsilicones such as aminoethylaminopropylsiloxane/dimethylsiloxanecopolymer, silanol-modified polysiloxanes, alkoxy-modifiedpolysiloxanes, aliphatic acid-modified polysiloxanes, fluorine-modifiedpolysiloxanes, epoxy-modified polysiloxanes, alkoxy-modifiedpolysiloxane perfluoropolyethers, polyvinyl acetate dimethylpolysiloxane and mixtures thereof.

The oil is preferably used in a ratio of about 10 to 99.9% by weightbased on the total weight of the gel composition. Where the amount ofthe oil is less than 10% by weight or more than 99.9% by weight,satisfactory gel strength may sometimes not be obtained.

The gel composition of the present invention may further contain anactive ingredient as an antiperspirant (hereinafter referred to as“antiperspirant active ingredient”). In the specification, the “anantiperspirant active ingredient” means an ingredient that suppressessweating by astringing the skin. However, the term should be construedin its widest sense, and the term must not be interpreted in anylimitative way. Type of the antiperspirant active ingredient is notparticularly limited, and two or more antiperspirant active ingredientsmay be used in combination. Examples of the antiperspirant activeingredient include chlorohydroxy aluminum, aluminum chloride, allantoinchlorohydroxy aluminum, aluminum sulfate, zinc oxide, zincparaphenolsulfonate, zirconium aluminum complex produced by reactingzirconyl chloride with aluminum hydroxide and aluminum chlorohydroxideand the like. The antiperspirant active ingredient can be formulated inan amount of 1 to 60% by weight, preferably 5 to 35% by weight, based onthe total weight of the gel composition. The antiperspirant activeingredient may be formulated in a form of either a solution or fineparticles. When the antiperspirant active ingredient is used in the formof fine particles, particle size of a substance as the antiperspirantactive ingredient may generally be about 1 to 100 microns, preferablyabout 1 to 50 microns, and said ingredient may preferably have a highbulk density.

Methods for producing the gel composition of the present invention arenot particularly limit. For example, a desired gel composition can beobtained by heating the aforementioned gelling agent and an oil to atemperature of about 50 to 180° C with stirring until the mixture becamea uniform solution, and then cooling the resulting solution.

The gel composition of the present invention can be used as a cosmetic.When the gel composition of the present invention is used as a cosmetic,the aforementioned gel composition per se may be used. Generally, it ispreferable to use the gel composition which is mixed with one or moretypes of ingredients ordinarily used for the manufacture of cosmetics.

Examples of ingredients to be formulated in cosmetics include, forexample, various chelating agents for maintaining the effect of theaforementioned antiperspirant active ingredient and suppressingdiscoloration or generation of odor and the like. Types of the chelatingagent are not particularly limited, and preferred examples thereofinclude chelating agents selected from the group consisting oftriethylenetetramine, 1,1,1-trifluoro-3,2′-thenoylacetone, thioglycolicacid, tartaric acid, succinic acid, 8-quinolinol,pyridine-2,6-dicarboxylic acid, pyridine, 1,10-phenanthroline, lacticacid, 8-hydroxyquinoline-5-sulfonic acid, glycine,2,2′-pyridylethylenediamine, Xylenol Orange, 5-sulfosalicylic acid,salicylic acid, pyrocatechol-3,5-disulfonate,4,5-dihydroxybenzene-1,3-disulfonic acid,1,2-diaminocyelohexane-N,N,N′,N′-tetraacetic acid, citric acid, oxalate,nitrilotriacetic acid, ethylenediamine-N,N,N′,N′-tetraacetic acid,acetylacetone and salts thereof, mixtures thereof and the like.

As other ingredients that can be formulated in cosmetics, one or morekinds of gelling agents other than the gelling agent of the presentinvention may be used in combination. Examples of such gelling agentsinclude polyamide resins, 12-hydroxystearic acid, sodium stearate,dibenzylidene-D-sorbitol, N-lauroyl-L-glutamic acid dibutylamide and thelike.

The cosmetic of the present invention may contain surfactants, variousadditives or various fine particles as other ingredients so far that theingredients do not affect the advantageous effects of the presentinvention. As the surfactants, any of anionic surfactants, nonionicsurfactants, cationic surfactants and ampholytic surfactants may beused. Examples of the anionic surfactants include, for example, N-longchain acyl amino acid salts such as N-long chain acyl acidic amino acidsalts and N-long chain acyl neutral amino acid salts, N-long chainaliphatic acid acyl-N-methyltaurine salts, alkyl sulfates and alkyleneoxide adducts thereof, aliphatic acid amide ether sulfates, metal saltsand weak base salts of aliphatic acids, sulfosuccinic acid typesurfactants, alkylphosphates and alkylene oxide adducts thereof, alkylether carboxylic acids and the like. Examples of the nonionicsurfactants include, for example, ether type surfactants such asglycerol ethers and alkylene oxide adducts thereof, ester typesurfactants such as glycerol esters and alkylene oxide adducts thereof,ether ester type surfactants such as sorbitan esters and alkylene oxideadducts thereof, ester type surfactants such as polyoxyalkylenealiphatic acid esters, glycerol esters, aliphatic acid polyglycerolesters, sorbitan esters and saccharose aliphatic acid esters,nitrogen-containing nonionic surfactants such as alkyl glucosides,hydrogenated castor oil pyroglutamic acid diesters and ethylene oxideadducts thereof, and aliphatic acid alkanolamides and the like. Examplesof the cationic surfactants include, for example, aliphatic amine saltssuch as alkylammonium chlorides and dialkylammonium chlorides,quaternary ammonium salts thereof, aromatic quaternary ammonium saltssuch as benzalkonium salts, aliphatic acid acyl arginine esters and thelike. Examples of the ampholytic surfactants include, for example,betaine type surfactants such as carboxybetaine, aminocarboxylic acidtype surfactants, imidazoline type surfactants and the like.

Examples of various additives include, for example, amino acids such asglycine, alanine, serine, threonine, arginine, glutamic acid, asparticacid, leucine and valine; polyhydric alcohols such as glycerol, ethyleneglycol, 1,3-butylene glycol, propylene glycol and isoprene glycol;polyamino acids including polyglutamic acid and polyaspartic acid andsalts thereof, water-soluble polymers such as polyethylene glycol, gumarabic, alginic acid salts, xanthane gum, hyaluronic acid, hyaluronicacid salts, chitin, chitosan, water-soluble chitin, carboxyvinylpolymers, carboxymethyl cellulose, hydroxyethyl cellulose,hydroxypropyltrimethyl ammonium chloride, poly(dimethylmethylenepiperidium chloride), quaternary ammoniums of polyvinylpyrrolidonederivatives, cationized proteins, collagen decomposition products andderivatives thereof, acylated proteins and polyglycerol; sugar alcoholssuch as mannitol and alkylene oxide adducts thereof; lower alcohols suchas ethanol and propanol as well as animal and plant extracts, nucleicacids, vitamins, enzymes, anti-inflammatory agents, antibacterialagents, preservatives, antioxidants, ultraviolet absorbers, chelatingagents, antiperspirants, pigments, dyes, oxidation dyes, organic andinorganic fine particles, pH adjusting agents, pearling agents, wettingagents and the like.

Examples of various fine particles include, for example, resin fineparticles such as nylon beads and silicone beads, nylon powder,aliphatic acid metal salt soap, yellow iron oxide, red iron oxide, blackiron oxide, chrome oxide, cobalt oxide, carbon black, ultramarine blue,Berlin blue, zinc oxide, titanium oxide, zirconium oxide, silicon oxide,aluminum oxide, cerium oxide, mica-titanium, boron nitride, bariumsulfate, calcium carbonate, magnesium carbonate, aluminum silicate,magnesium silicate, silicon carbide, dyes, lakes, sericite, mica, talc,kaolin, tabular barium sulfate, butterfly-shaped barium sulfate,microparticle titanium oxide, microparticle zinc oxide, microparticleiron oxide, acylamino acids such as acyllysine, acylglutamic acid,acylarginine and acylglycine and the like. Examples of usable fineparticles also include the aforementioned fine particles which aresubjected to a surface treatment such as silicone treatment,fluoro-compound treatment, silane coupling agent treatment, silanizedorganic titanate treatment, acylated lysine treatment, aliphatic acidtreatment, metallic soap treatment, oil treatment, amino acid treatmentand the like.

Purposes of use of the cosmetic of the present invention are notparticularly limited. For example, the cosmetic can be used as acosmetic in a form of, for example, a gel, a pack, a granule and thelike. The cosmetic of the present invention can be manufactured bypreparing the aforementioned gel composition, then adding and mixing oneor more kinds of the additives explained above as required to form auniform composition. Processes for the manufacture are not particularlylimited, and any means available to those skilled in the art such ascommonly and widely used means including mixing, stirring and kneadingcan be appropriately used.

EXAMPLES

The present invention will be explained more specifically with referenceto the following examples. However, the present invention is not limitedto the following examples.

Example 1 Preparation of N-2-(R,S)-ethylhexanoyl-L-glutamic aciddibutylamide

110 g of sodium glutamate monohydrate was dissolved in 140 g of waterand 78 g of 27% aqueous sodium hydroxide and the solution was cooled to10° C. The solution was added with 110 g of acetone and added dropwisewith 87 g of 2-ethylhexanoyl chloride and 78 g of 27% aqueous sodiumhydroxide. The reaction mixture for the acylation was diluted with 100 gof water and neutralized with 63 g of 95% sulfuric acid to separate anoil. The aqueous layer was removed, and the oil layer was concentratedunder reduced pressure to obtain an oily substance. The resulting oilysubstance was dissolved in 742 g of methanol, and the solution was addedwith 6.2 g of 95% sulfuric acid and refluxed for 9 hours. The reactionmixture was left stand for cooling to 35° C. and neutralized with 8.8 gof n-butylamine, and then the methanol was evaporated to obtain an oilysubstance. The resulting oily substance was added with 643 g of tolueneand 271 g of n-butylamine and the mixture was stirred with heating at90° C. for 10 hours. The reaction mixture was added with 506 g of warmwater and 130 g of 95% sulfuric acid to separate an oil, and the aqueouslayer was removed. The oil layer was added with 1200 g of warm water,and the solvent was removed under ordinary pressure to obtain slurry ofwhite solid. This solid was collected by filtration and dried in vacuoat 50° C. to obtain 2-ethylhexanoylglutamic acid dibutylamide.

(a) ¹³C-NMR peaks (solvent: CDCl₃): 12.04, 12.07, 13.74, 13.96, 13.99,20.08, 20.11, 22.70, 22.74, 26.01, 29.83, 31.56, 31.60, 32.37, 33.05,39.29, 39.53, 49.37, 52.53, 52.56, 171.29, 173.03, 176.66 (ppm)

(b) ¹H-NMR peaks (CDCl₁₃) δ: 3.248 (m, 4H), 4.373 (m, 1H), 6.199 (brs,1H), 7.079 (brs, 1H), 7.169 (brs, 1H)

(c) Wave number of infrared absorption spectrum: 3291.7, 2961.0, 2932.5,1638.2, 1551.2, 1452.6 (cm⁻¹)

(d) MS: 382.3 (M−H)⁻

Example 2 Preparation of N-octanoyl-L-glutamic acid dibutylamide

110 g of sodium glutamate monohydrate was dissolved in 140 g of waterand 78 g of 27% aqueous sodium hydroxide and cooled to 10° C. Thesolution was added with 110 g of acetone and added dropwise with 87 g ofoctanoyl chloride and 90 g of 27% aqueous sodium hydroxide. The reactionmixture for the acylation was diluted with 100 g of water andneutralized with 64 g of 95% sulfuric acid to separate an oil, Theaqueous layer was removed, and the oil layer was concentrated underreduced pressure to obtain an oily substance. The resulting oilysubstance was dissolved in 742 g of methanol, and the solution was addedwith 6.2 g of 95% sulfuric acid and refluxed for 9 hours. The reactionmixture was left stand for cooling to 35° C. and neutralized with 10.5 gof n-butylamine, and then the methanol was evaporated to obtain an oilysubstance. The resulting oily substance was added with 630 g of tolueneand 191 g of n-butylamine and the mixture was stirred with heating at90° C. for 10 hours. The reaction mixture was added with 500 g of warmwater and 178 g of 95% sulfuric acid to separate an oil, and the aqueouslayer was removed. The oil layer was added with 645 g of warm water, andthe solvent was removed under ordinary pressure to obtain slurry ofwhite solid. The resulting solid was collected by filtration and driedin vacuo at 50° C. to obtain octanoylglutamic acid dibutylamide.

(a) ¹³C-NMR peaks: 14.10, 14.43, 20.44, 22.98, 26.07, 29.38, 29.61,29.86, 31.92, 31.97, 32.06, 33.44, 37.07, 39.69, 39.88, 52.91, 171.61,173.33, 174.17 (ppm)

(b) ¹H-NMR peaks (CDCl₃) δ: 3.247 (m,4H),4.360 (m, 1H), 6.201 (brs, 1H),6.987 (brs, 1H), 7.039 (brs, 1H)

(c) Wave number of infrared absorption spectrum: 3292.8, 2958.3, 2930.4,1640.1, 1543.0, 1450.3 (cm⁻¹)

(d) MS: 382.3 (M−H)⁻¹

Example 3 Preparation method of N-decanoyl-L-glutamic acid dibutylamide

In a manner similar to that of the aforementioned Example 1,N-decanoyl-L-glutamic acid dibutylamide was prepared.

(a) ¹³C-NMR peaks: 14.10, 14.47, 20.44, 20.48, 23.04, 26.07, 29.65,29.67, 29.73, 29.83, 29.88, 31.92, 31.97, 32.24, 37.08, 39.70, 39.88,52.90, 171.60, 173.33, 174.17 (ppm)

(b) ¹H-NMR peaks (CDCl₃) δ: 3.250 (m, 4H), 4.360 (m, 1H), 6.190 (brs,1H), 6.980 (brs, 1H), 7.030 (brs, 1H)

(c) Wave number of infrared absorption spectrum: 3294.8, 2959.0, 2927.5,1637.9, 1556.0, 1466.6 (cm⁻¹)

(d) MS: 410.5 (M−H)⁻

Ethyloylglutamic acid dibutylamide, hexanoylglutamic acid dibutylamide,myristoylglutamic acid dibutylamide and palmitoylglutamic aciddibutylamide used in the following comparative examples were produced ina similar manner.

Examples 4 to 6 Preparation of Gel Compositions

0.2 g of each N-acylglutamic acid dibutylamide shown in Table 1 wasadded to 20 g of each oil and dissolved by heating on an oil bath at150° C., and then the resulting solution was left stand at 23° C. for 15hours for cooling to obtain each gel composition. Gel strength of eachof the resulting gel compositions was measured by using a rheometer(FUDOH RHEO METER NRM-2010-J-CW). An adapter for plume andviscoelasticity, 10 φ, was used, and the sample stage velocity was 6cm/min. The results are shown in Table 1. As clearly understandable fromthe results shown in Table 1, N-2-(R,S)-ethylhexanoyl-L-glutamic aciddibutylamide, N-octanoyl-L-glutamic acid dibutylamide andN-decanoyl-L-glutamic acid dibutylamide have higher gel forming abilitythan the other gelling agents and can exert superior gel forming abilityirrespective of a type of an oil. TABLE 1 Gelling ability of variousN-acylglutamic acid dibutylamides Gel Liquid composition Acyl group IPMTOG paraffin Example 4 Octanoyl 99 156 136 Example 5 2-Ethylhexanoyl 175209 145 Example 6 Decanoyl 120 183 154 Comparative Acetyl 18 48Insoluble Example 1 Comparative Hexanoyl Not gelled Not gelled InsolubleExample 2 Comparative Dodecanoyl 95 116 92 Example 3 (lauroyl)Comparative Tetradecanoyl 67 72 80 Example 4 (myristoyl) ComparativePentadecanoyl — — 30 Example 5IPM: Isopropyl myristateTOG: Triocanoic acid glycerideUnit: gel strength (g/cm²)

Examples 7 to 10 Preparation of Gel Compositions

0.4 g of each gelling agent shown in Table 2 was added to 20 g of an oiland dissolved by heating on an oil bath at 150° C., and then theresulting solution was left stand at 23° C. for 15 hours for cooling toobtain gel compositions. Gel strength of each of the resulting gelcompositions was measured by using a rheometer (FUDOH RHEO METERNRM-2010-J-CW). An adapter for plume and viscoelasticity, 10, was used,and the sample stage velocity was 6 cm/min. Further, transparency ofeach of the resulting gel compositions was determined by visualinspection. The results are shown in Table 2. It is understandable thatthe gel compositions of Examples 7 to 9 have higher gel strength thanthe gel compositions of Comparative Examples 6 to 8. Further, it is alsounderstandable that the gel compositions of Examples 8 to 10 have highertransparency than the gel compositions of the comparative examples.TABLE 2 Gelling ability of various N-acylglutamic acid dibutylamidesComparative Comparative Comparative Example 7 Example 8 Example 9Example 10 Example 6 Example 7 Example 8 N-2-Ethylhexanoylglutamic 0.40.3 0.2 0.1 — — — acid dibutylamide (Compound of Example 1)N-Lauroylglutamic acid — 0.1 0.2 0.3 0.4 0.15 — dibutylamide12-Hydroxystearic acid — — — — — 0.25 0.4 Octyldodecanol 4 4 4 4 4 4 4Cyclometicon D-5* 16 16 16 16 16 16 16 Gel strength (g/cm²) 650 380 400190 330 280 0 Transparency Opaque Translucent Translucent TranslucentOpaque Opaque Opaque*TORAY-DOW CORNING SILICONE CORP., SH245

Examples 11 and 12 Preparation of Antiperspirant Gel Sticks

Each gelling agent shown in Table 3 was dissolved in an oil by heating,then the resulting solution added with aluminum zirconiumtrichlorohydrex glycine and left for cooling with stirring to obtain anantiperspirant gel stick. Gel strength of each of the resultingantiperspirant gel sticks was measured by using a rheometer (FUDOH RHEOMETER NRM-2010-J-CW). An adapter for plume and viscoelasticity, 10 φ,was used, and the sample stage velocity was 6 cm/min. The results areshown in Table 3. The results indicate that the gel sticks of Examples11 and 12 have higher gel strength than the gel sticks of thecomparative example, and thus superior antiperspirants is obtainable.TABLE 3 Gelling ability of various N-acylglutamic acid dibutylamidesComparative Example 9 Example 11 Example 12 N-Lauroylglutamic acid 2 1 —dibutylamide N-2-Ethylhexanoylglutamic — 1 2 acid dibutylamide (Compoundof Example 1) 12-Hydroxystearic acid 7 7 7 Octyldodecanol 14 14 14Cyclometicon D-5* 48 48 48 Aluminum zirconium 26 26 26 trichlorohydrexglycine Gel strength (g/cm²) 1847 2250 2650*TORAY-DOW CORNING SILICONE CORP., SH245**Westwood Chemical Corporation, Westchlor ZR 30B DM CP-5

Example 13 Preparation of Lipstick

A lipstick was prepared in a conventional manner by using thecomposition shown in Table 4. TABLE 4 Lipstick Example 13 Octylpalmitate 14 Lanolin 8.5 Isopropyl palmitate 8.5 Cetyl ricinoleate 5Dimeric acid isopropyl ester 13 N-2-Ethylhexanoylglutamic aciddibutylamide 1.5 Red No. 223 12 Lecithin 0.7 Polyethylene glycoldistearate 3.25 Sorbitan monooleate 5 Choresteryl hydroxystearate 2Dipentaerythritol 2 Glycerol 9 Panthenol 1 Ozokerite 3.5 Paraffin 3.25Candelilla wax 4.65 Bees wax 3 Tocophenol 0.1 Propylparaben 0.05 (Weight%)

The lipstick obtained was superior in strength and excellently free fromsweating.

Example 14 Preparation of Transparent Lipstick

A transparent lipstick was prepared in a conventional manner by usingthe composition shown in Table 5. TABLE 5 Stick type transparentlipstick Example 14 N-2-Ethylhexanoylglutamic acid dibutylamide 3Aliphatic acid starch ester 5 12-Hydroxystearic acid 1.5 Diglyceryltriisostearate 80.45 Rosin acid pentaerythritol ester 10 Red No. 2230.05 (Weight %)

The transparent lipstick obtained was superior in strength, andmoreover, had highly transparent appearance and satisfactory stability.

Example 15 Preparation of Candle

A candle was prepared in a conventional manner by using the compositionshown in Table 6. TABLE 6 Candle Example 15 Hydrogenated polyisobutene*87.4 Hydrogenated polyisobutene** 6.7 Isostearyl alcohol 5.5N-2-Ethylhexanoylglutamic acid dibutylamide 0.4 (Weight %)*Panalane ™ H300E (Amoco Chemical)**Panalane ™ L14E (Amoco Chemical)

The candle obtained was superior in strength and had highly transparentappearance.

1. A gel composition comprising: (a) N-2-ethylhexanoyl-L-glutamic aciddibutylamide, and (b) a silicone oil.
 2. The gel composition accordingto claim 1, wherein said silicone oil is one or more silicone oilsselected from the group consisting of methylpolysiloxane, highlypolymerized methylpolysiloxane, ether-modified silicones,stearoxymethylpolysiloxane, stearoxytrimethylsilane, methyl hydrogenpolysiloxane, octamethylpolysiloxane, decamethylpolysiloxane, cyclicsilicones, methylphenylpolysiloxane, trimethylsiloxy silicate,amino-modified silicones, silanol-modified polysiloxanes,alkoxy-modified polysiloxanes, aliphatic acid-modified polysiloxanes,fluorine-modified polysiloxanes, epoxy-modified polysiloxanes,alkoxy-modified polysiloxane perfluoropolyethers, and polyvinyl acetatedimethyl polysiloxane.
 3. The gel composition according to claim 1,wherein said silicone oil is a cyclic silicone.
 4. The gel compositionaccording to claim 1, wherein said silicone oil is one or more siliconeoils selected from the group consisting of decamethylcyclopentasiloxane,octamethylcyclotetrasiloxane, tetrahydrotetramethylcyclotetrasiloxane,methylcyclopolysiloxane, cyclopentasiloxane anddodecamethylcyclohexasiloxane.
 5. The gel composition according to claim1, wherein said silicone oil is a methylcyclopolysiloxane.
 6. The gelcomposition according to claim 1, wherein said silicone oil is adecamethylcyclopentasiloxane.
 7. The gel composition according to claim1, further comprising an antiperspirant.
 8. The gel compositionaccording to claim 7, wherein said antiperspirant is at least oneselected from the group consisting of chlorohydroxy aluminum, aluminumchloride, allantoin chlorohydroxy aluminum, aluminum sulfate, zincoxide, zinc paraphenolsulfonate, zirconium aluminum complex produced byreacting zirconyl chloride with aluminum hydroxide, and aluminumchlorohydroxide.
 9. The gel composition according to claim 7, whereinthe amount of the antiperspirant ranges from 1 to 60% by weight based onthe total weight of the gel composition.
 10. The gel compositionaccording to claim 7, wherein the amount of the antiperspirant rangesfrom 5 to 35% by weight based on the total weight of the gelcomposition.
 11. The gel composition according to claim 7, wherein theantiperspirant is in the form of fine particles.
 12. The gel compositionaccording to claim 11, wherein the fine particles have a particle sizeranging from 1 to 100 microns.
 13. The gel composition according toclaim 11, wherein the fine particles have a particle size ranging from 1to 50 microns.
 14. The gel composition according to claim 1, which is atranslucent composition.
 15. The gel composition according to claim 1,wherein the amount of the N-2-ethylhexanoyl-L-glutamic acid dibutylamideranges from 0.1 to 15 parts by weight based on the oil to be gelled. 16.The gel composition according to claim 1, wherein the amount of theN-2-ethylhexanoyl-L-glutamic acid dibutylamide ranges from 1 to 10 partsby weight based on the oil to be gelled.
 17. The gel compositionaccording to claim 1, wherein the amount of the silicone oil ranges from10 to 99.9% by weight based on the total weight of the gel composition.18. The gel composition according to claim 1, further comprising ahigher alcohol.
 19. The gel composition according to claim 18, whereinsaid higher alcohol is at least one selected from the group consistingof cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcoholand octyldodecanol.
 20. The gel composition according to claim 18,wherein said higher alcohol is a octyldodecanol.
 21. A cosmeticcomprising a gel composition according to claim
 1. 22. The cosmeticaccording to claim 21, further comprising one or more additives selectedfrom the group consisting of a chelating agent, a gelling agent, asurfactant, an amino acid, a polyhydric alcohol, a polyamino acid, awater-soluble polymer, a sugar alcohol, a lower alcohol, an animalextract, a plant extract, a nucleic acid, a vitamin, an enzyme, ananti-inflammatory agent, an antibacterial agent, a preservative, anantioxidant, an ultraviolet absorber, an antiperspirant, a pigment, adye, an oxidation dye, an organic fine particle, an inorganic fineparticle, a pH adjusting agent, a pearling agent, and a wetting agent.